Insecticide



- tural insect pests.

1 msnc'rrcrns Gerald B. Coleman, Fred W. Fletcher, and Wesley D. Sohroe der, Midland, Mich,

minors to The Dow Chemical Company, Midland, Mich, a corporation of Michigan No Drawing. Application October 2t, K941i,

Serial No. M8371 '1 cuss. goi. row-2s) This invention relates to insecticides and is particularly directed to new compositions of matter adapted to be employed as contact poisons for the control of household and agricultural parasites.

According to the present'invention an alkyl or allrenyl ether oi. 3.fix trichloro-z-hydroxy-diphenyl is componded with a suitable inert carrier and/or compatible parasiticidal toiticant to obtain a composition adapted to be employed for the control of common household and agricul- Comitions in which the new ether compounds are employed as active toxicants are characterized by a high effectivenear when applied as-contact poisons. The new ether compounds as a class are substantially insoluble in water, somewhat soluble in many orgarlic solvents, and sumciently inert as not to react with other hno insecticidal tonicants. The compounds are high boiling liquids or low melting crystalline solids, stable on, exposure to light, air, and water, lacking in objectionable odor, and relatively nonirfltating and nontoxic to higher forms oil 11-" l, s. lite.

Compositions comprising from about 2 to ill per cent by weight of these others dissolved in a noncorrosive organic solvent may he advantaseously employed as fly sprays, moth prooiers, roach sprays, and the like. For the control of agricultural pests such as red spider, aphls, etc., the compounds are preferably employed in aqueousdispersions or as the constituents of finelydivided dust compositions. in preparing aqueous spray mixtures, the compounds may simply be dispersed in water. A preferred procedure comprises mixing the toxicant with or depositing it on a water-insoluble, finely-divided solid carrier to term a concentrate, and thereafter dispersing the dry compositionin water. An ultimate concentration of from about our to ll per cent by weight oi the tonicant in the aqueous composition is adequate. In preparing dust compositions, the proportion of tot employed is dependent upon whether or notthe dust is to he used as-a concentrate iorthe preparation oi aqueous dispersions or applied for pest control without further modification. it a concentrate is desired,

from shout to to to per cent by weight or the toricant may he ploycd, depending own the physical nature or the particular ether and carrier selected. lln t me dusting compositions from about us to 5.0 percent oi toricant is preferred.

The ether tonicant may combined with other advantageously ,he "ticidal materials such as pyrethrinor rotenone-containing extracts, lead arsenate, petroleum oil, organic thiocyanates,

etc. en, mixtures of the ethe'rs with the plant extract toxlcants are employed, a. greater than additive efiect as regards toxicity is obtained for wherein the ether toxicants are dissolved or dispersed in either the continuous or discontinuous phase oi emulsions.

in the preparation of concentrates and dust compositions, carriers; such as bentonite, diatomaceous earth lrieselguhr, volcanic ash, pyrophyllite, talc, wood flour, finely-divided carbon. and the like may be employed. Wetting agents which may be incorporated in either liquid or dust compositions include the alkali and allraline earth metal caseinates, blood albumen,

alkali metal salts of long chain aliphatic sulphates partially neutralized sulphuric acid derivutives of petroleum oils and natural occurring glycerides sulphonated derivatives of phenols and aromatic hydrocarbons and their salts, soaps,

condensation products of allsylene oxides with organic acids, allranolamines, etc.

The following examples are illustrative of certain' modes in which the invention may be employed but are not to be construed as limiting the some. I

Example 1 point of 137 F. This composition was employed as a spray against five-day old houseflies'accordins to the Feet-Grady method (Soap ll, No. it, 1932). The composition was found to give a 30% per cent hill or the flies in so hours. A deteination was also carried out on an analogous solution comprising ass grams-oi the methyl ether of 3.5.x-trichloro-2-hydrory-diplienyland 5d millig or pyrethrins per milliliters of'soi lotion. This composition killed the percent oi the dies in to hours. A petroleum distillate con:

trol solution containing 50 milligrams of pyrethrin as the sole toxicant per 100 milliliters gave an average kill of 25 per cent against houseflies.

Example 2 The ethyl ether of 3.5;x-trichloro-2-hydroxydiphenyl (melting at 61-63 C.) was employed to produce a spray mixture substantially as described in Example 1 except that the 2.48 grams of ether was first dissolved in milliliters of methyl ethyl ketone and thereafter made up to a volume of 100 milliliters with the petroleum disti1late.= I This composition gavev a 'kill against housefiies of 24.1 per cent in 2'. hours. when modified by the inclusion of 50 milligrams of D?- rethrins per 100 milliliters, the composition gave a kill of 59.8 per cent.

Example 3 In a similar manner, the normalbutyl ether oi 3.5.x-trichioro 2-hydroxy-diphenyl (boiling at 177-1'l9 C. at 1.5 millimeters pressure and having a specific gravity of 1.266 at /25 C.) was employed in petroleum distillate solution both alone and in combination with pyrethrins. In a mixture of 2.48 grams to 100 milliliters, this compound gave a kill of 20.6 per cent. A combination with the usual amount of pyrethrin gave a composition killing 52.3 per cent of the test insects.

Example 4 2.48 grams of the allyl ether of 3.5.x-trichloro- 2-hydroxy-diphenyl (boiling at 206-209 C. at 4 millimeters pressure) was dissolved in 20 milliliters of methyl ethyl ketone and the resulting solution diluted with sufiicient of the petroleum larly, the disclosed compositions and other mix-.

tures comprising the new toxicants may be employed for the control or other household pestsand agricultural insect organisms.

The expression "noncorrosive organic solvent as herein em'ployed'refers to any organic solvent -material unreactive with and capable oi! dissolving the toxicants' hereinbefore described and non- These compounds are prepared by reacting a suitable etherifying agent such as an organic sulphate, alkyl or a'lkenyl halide, etc., in the Presence of an alkali metal hydroxide.

The 3.5.x-trichloro-2-hydroxy-diphenyl employed in the preparation of the ethers is obtained by reacting Z-hydroxy-dlphenyl with gasindicated the reaction of-3 mols of chlorine. The

crude reaction product solidified upon cooling, and was dissolved in hot petroleum ether and recrystallized. After several recrystallizations there was obtained a 49 percent yield of 3.5.x-trichloro- 2-hydroxy-diphenyl as a white solid melting at 117-118.5 C. This compound was substantially insoluble in water, slightly'soluble in kerosene, and somewhat soluble in carbon tetrachloride and 95 pe'r cent ethyl alcohol. Upon analysis, the phenol wastound to'contain 38.95 per cent chlorine as compared to a theoreticalchlorlne contentof 39 per cent. The position of the third chlorine atom in the hydroxylated benzene ring was determined by the oxidation of the compound to iorm benzoic acid.

We claim:

1. An insecticidal composition comprising a car-- phenyl.

2. An insecticidal composition comprising an inert diluent and as an active toxicant a comlulurious to the skin and gener'al health of humans under the conditions of use.

The ether compounds with which the present application is concerned are described and pound selected from the group consisting of the alkyl and alkenyl ethers of 3.5.x-trich1oro-2-hydroxy-diphenyl. v

3. An insecticidal composition comprising as an'active toxicant a compound selected from the group consisting of alkyl and alkenyl ethers of 3.5.x-trichloro 2-hydroxy-diphenyl dissolved in a noncorrosive organic solvent.

4. An insecticidal composition comprising an inert diluent and as an active toxicant the methyl ether of 3.5.x-triehIoro-2-hydroxy-diphenyl.

5. An insecticidal composition comprising an inert diluent and as an active toxlcant the ethyl ether 01' 3.5.x-trichloro-2-hydroxy-diphenyl.

8. An insecticidal composition comprising an inert diluent and as an active toxicant the alkenyl ether of 3.5.x-trichloro-2-hydron-diphenyl.

7; An insecticidal composition comprising pyrethrins and as an added toxicant a compoimd selected tromthegroupconsistingofalkylandalkyenyl ethers of 3.5.x-trichloro-2-hydroxy-diphenyl. GERALD H. COLEMAN.

, FRED W. 

